III syllabus 2014-15

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GIRRAJ GOVT. COLLEGE,(AUTONOMOUS) NIZAMABAD
DEPARTMENT OF CHEMISTRY
III YEAR SYLLABUS
V SEMESTER
Unit – I (Inorganic Chemistry)
(1 h/w)
1. Coordination Chemistry: IUPAC nomenclature, bonding theories – review of Werner’s
theory and Sidgwick’s concept of coordination, Valence bond theory, geometries of coordination
numbers 4-tetrahedral and square planar and 6-octahedral and its limitations, crystal filed theory,
splitting of d-orbitals in octahedral, tetrahedral and square-planar complexes – low spin and high
spin complexes – factors affecting crystalfield splitting energy, merits and demerits of crystalfield theory. Isomerism in coordination compounds – structural isomerism and stereo isomerism,
stereochemistry of complexes with 4 and 6 coordination numbers.
2. Spectral and magnetic properties of metal complexes: Electronic absorption spectrum of
[Ti(H2O)6]3+ ion. Types of magnetic behavior, spin-only formula, calculation of magnetic
moments, experimental determination of magnetic susceptibility – Gouy method
UNIT – II (Organic Chemistry )
(1h/w)
1. Nitrogen compounds 9 h
Nitro hydrocarbons: Nomenclature and classification – nitro hydrocarbons – structure.
Tautomerism of nitroalkanes leading to aci and keto form. Preparation of Nitroalkanes.
Reactivity – halogenation, reaction with HONO (Nitrous acid), Nef reaction and Mannich
reaction leading to Michael addition and reduction. Amines (Aliphatic and Aromatic):
Nomenclature, Classification into 10, 20, 30 Amines and Quarternary ammonium compounds.
Preparative methods -1. Ammonolysis of alkylhalides 2. Gabriel synthesis 3. Hoffman’s
bromamide reaction (mechanism). 4. Reduction of Amides and Schmidt reaction. Physical
properties and basic character – Comparative basic strength of Ammonia, methyl amine,
dimethyl amine, trimethyl amine and aniline – comparative basic strength of aniline, Nmethylaniline and N,N-dimethyl aniline (in aqueous and non-aqueous medium), steric effects
and substituent effects. Use of amine salts as phase transfer catalysts.
Chemical properties: a) Alkylation b) Acylation c) Carbylamine reaction d) Hinsberg separation
e) Reaction with Nitrous acid of 10, 20, 30 (Aliphatic and aromatic amines). Electrophilic
substitutions of Aromatic amines – Bromination and Nitration. oxidation of aryl and 30 Amines.
Diazotization Cyanides and isocyanides: Nomenclature (aliphatic and aromatic) structure.
Preparation of cyanides from a) Alkyl halides b) from amides c) from aldoximes. Preparation of
isocyanides from Alkyl halides and Amines. Properties of cyanides and isocyanides, a)
hydrolysis b) addition of Grignard reagent iii) reduction iv) oxidation.
2. Amino acids and proteins 5 h
Introduction: Definition of Amino acids, classification of Amino acids into alpha, beta, and gama
amino acids. Natural and essential amino acids – definition and examples, classification of alpha
amino acids into acidic, basic and neutral amino acids with examples. Methods of synthesis:
General methods of synthesis of alpha amino acids (specific examples – Glycine, Alanine, valine
and leucene) by following methods: a) from halogenated carboxylic acid b) Malonic ester
synthesis c) strecker’s synthesis. Physical properties: Optical activity of naturally occurring
amino acids: L-configuration, irrespective of sign rotation, Zwitterion structure – salt like
character - solubility, melting points, amphoteric character , definition of isoelectric point.
Chemical properties: General reactions due to amino and carboxyl groups – lactams from gamma
and delta amino acids by heating peptide bond (amide linkage). Structure and nomenclature of
peptides and proteins.
Unit-III (physical chemistry)
(1 h / w)
1. Chemical kinetics 9 h
Rate of reaction, factors influencing the rate of a reaction-concentration, temperature, pressure,
solvent, light, catalyst. Experimental methods to determine the rate of reaction. Definition of
order and molecularity. Derivation of rate constants for first, second, third and zero order
reactions and examples. Derivation for time half change. Methods to determine the order of
reactions. Kinetics of complex reactions (first order only): opposing reactions, parallel reactions,
consecutive reactions and chain reactions. Effect of temperature on rate of reaction, Arrhenius
equation, concept of activation energy. Theories of reaction rates- collision theory-derivation of
rate constant for bimolecular reaction. The transition state theory (elementary treatment).
Unit-IV (General chemistry)
(1 h / w)
1. Heterocyclic Compounds 5 h
Introduction and definition: Simple 5 membered ring compounds with one hetero atom Ex.
Furan. Thiophene and pyrrole. Importance of ring system – presence in important natural
products like hemoglobin and chlorophyll. Numbering the ring systems as per Greek letter and
Numbers. Aromatic character – 6- electron system (four-electrons from two double bonds and a
pair of non-bonded electrons from the hetero atom). Tendency to undergo substitution reactions.
Resonance structures: Indicating electron surplus carbons and electron deficient hetero atom.
Explanation of feebly acidic character of pyrrole, electrophillic substitution at 2 or 5 position,
Halogenation, Nitration and Sulphonation under mild conditions. Reactivity of furan as 1,3diene, Diels Alder reactions (one example). Sulphonation of thiophene purification of Benzene
obtained from coal tar). Preparation of furan, Pyrrole and thiophene from 1,4,- dicarbonyl
compounds only, Paul-Knorr synthesis, structure of pyridine, Basicity – Aromaticity –
Comparison with pyrrole – one method of preparation and properties – Reactivity towards
Nucleophilic substitution reaction – chichibabin
reaction.
2. Photochemistry 5 h
Difference between thermal and photochemical processes. Laws of photochemistry- GrothusDraper’s law and Stark-Einstein’s law of photochemical equivalence. Quantum yield.
Ferrioxalate actinometry. Photochemical hydrogen- chlorine, hydrogen-bromine reaction.
Jablonski diagram depicting various processes occurring in the excited state, qualitative
description of fluorescence, phosphorescence, non-radiative processes (internal conversion,
intersystem crossing). Photosensitized reactions- energy transfer processes (simple example).
LABORATORY COURSE – III
Practical Paper – III (Organic Chemistry) 90 hrs (3 h / w)
1. Synthesis of Organic Compounds
i. Aromatic electrophilic substitution Nitration: Preparation of nitro benzene and p-nitro
acetanilide, Halogenation: Preparation of p-bromo acetanilide – preparation of 2,4,6-tribromo
phenol.
ii. Diazotization and coupling: Preparation of pheyl azo β-napthol
iii. Oxidation: Preparation of benzoic acid from benzoyl chloride
iv. Reduction: Preparation of m-nitro aniline from m-dinitro benzene
v. Esterfication: Preparation of methyl p-nitro benzoate from p-nitro benzoic acid.
vi. Methylation: Preparation of β-napthyl methyl ether
Condensation: Preparation of benzilidine aniline and Benzoyl aniline.
2. Thin layer Chromatography & Column Chromatography
i. Preparation of the TLC plates. Checking the purity of the compounds by TLC:
Acetylation of salicyclic acid, aniline, Benzoylation of Aniline and Phenol Determination of Rf
values and identification of organic compounds by TLC: preparation and separation of 2,4dinitrophenyl hydrazones of acetione and 2-butanone using toluene and light petroleum(40:60)
ii. Separation of ortho & para nitro aniline mixture by column chromatography
3. Organic Qualitative Analysis:
i. Identification of an organic compound through the functional group analysis, determination
of melting point and preparation of suitable derivatives.
ii. Separation of two component mixtures
1) Aniline + Naphthalene 2) Benzoic acid + Benzophenone 3) p-Cresol + Chlorobenzene.
4. Demonstration experiments:
1. Steam distillation experiment: separation of ortho and para nitro phenols 2) Microwave
assisted Green synthesis, two examples: 1. Hydrolysis of Benzamide 2. Oxidation of Toluene
LABORATORY COURSE – IV
Practical Paper IV (Physical Chemistry) 90hrs (3 h / w)
1. Chemical kinetics
i. Determination of specific reaction rate of the hydrolysis of methyl acetate catalyzed by
hydrogen ion at room temperature.
ii. Determination of rate of decomposition of hydrogen peroxide.
iii. Determination of overall order of saponification of ethyl acetate
2. Distribution law
i. Determination of distribution coefficient of iodine between water and carbon Tetrachloride.
ii. Determination of molecular status and partition coefficient of benzoic acid in Toluene and
water.
3. Electrochemistry
i. Determination of concentration of HCl conductometrically using standard NaOH solution.
ii. Determination of concentration of acetic acid conductometrically using standard NaOH
solution.
iii. Determination of dissociation constant (Ka) of acetic acid by conductivity measurements.
iv. Determination of solubility and solubility product of BaSO4.
v. Determination of redox potentials of Fe2+/Fe3+by potentiometric titration of ferrous
ammonium sulphate vs. potassium dichromate.
4. pH metry
i. Preparation phosphate buffer solutions
ii. pH metric titration of weak acid, acetic acid with strong base NaOH and calculation of
dissociation constant.
5. Colorimetry
i. Verification of Beer-Lambert law for KMnO4 , K2Cr2O7 and determination of concentration of
the given solution.
ii. Verification of Beer-Lambert law for CuSO4 and determination of concentration of the given
solution.
iii. Composition of complex of Cu2+ - EDTA disodium salt
6. Adsorption
i. Surface tension and viscosity of liquids.
ii. Adsorption of acetic acid on animal charcoal, verification of Freundlich isotherm.
7. Project Work:
Collection of spectral data of a minimum of six compounds belonging to different functional
groups (other than those included in the syllabus) and submission of the report.
NOTE: Apart from the experiments (1 to 6) the project work (7) shall also be included in the
University Examination.
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